Binder

ABSTRACT

The present invention relates to binder compositions with an improved amine component, and a method of manufacturing a collection of matter bound by said binder compositions.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.16/434,072, filed Jun. 6, 2019, which is a continuation of U.S.application Ser. No. 15/714,150 (now U.S. Pat. No. 10,508,172), filedSep. 25, 2017, which is a continuation of U.S. application Ser. No.14/649,452 (now abandoned), filed Jun. 3, 2015, which is a U.S. nationalcounterpart application of International Application Serial No.PCT/EP2013/075378, filed Dec. 3, 2013, under 35 U.S.C. § 371, whichclaims priority to GB Application Serial No. 1221873.1, filed Dec. 5,2012, the entire disclosures of which are expressly incorporated byreference herein.

TECHNICAL FIELD

The present invention relates to binder compositions with an improvedamine component, and a method of manufacturing a collection of matterbound by said binder compositions.

BACKGROUND

Generally, binders are useful in fabricating articles because they arecapable of consolidating non- or loosely-assembled matter. For example,binders enable two or more surfaces to become united. In particular,binders may be used to produce products comprising consolidated fibers.Thermosetting binders may be characterized by being transformed intoinsoluble and infusible materials by means of either heat or catalyticaction. Examples of a thermosetting binder include a variety ofphenol-aldehyde, urea-aldehyde, melamine-aldehyde, and othercondensation-polymerization materials like furane and polyurethaneresins. Binder compositions containing phenol-aldehyde,resorcinol-aldehyde, phenol/aldehyde/urea, phenol/melamine/aldehyde, andthe like are widely used for the bonding of fibers, textiles, plastics,rubbers, and many other materials.

The mineral wool and fiber board industries have historically used aphenol formaldehyde binder to bind fibers. Phenol formaldehyde typebinders provide suitable properties to the final products; however,environmental considerations have motivated the development ofalternative binders. One such alternative binder is a carbohydrate basedbinder derived from reacting a carbohydrate and a multiprotic acid, forexample, U.S. Published Application No. 2007/0027283 and Published PCTApplication WO2009/019235. Another alternative binder is theesterification products of reacting a polycarboxylic acid and a polyol,for example, U.S. Published Application No. 2005/0202224. Because thesebinders do not utilize formaldehyde as a reagent, they have beencollectively referred to as formaldehyde-free binders.

One area of current development is to find a replacement for the phenolformaldehyde type binders across the entire range of products in thebuilding and automotive sector (e.g. fiberglass insulation, particleboards, office panels, and acoustical sound insulation). In particular,the previously developed formaldehyde-free binders may not possess allof the desired properties for all the products in this sector. Forexample, acrylic acid and poly(vinylalcohol) based binders have shownpromising performance characteristics. However, these are relativelymore expensive than phenol formaldehyde binders, are derived essentiallyfrom petroleum-based resources, and have a tendency to exhibit lowerreaction rates compared to the phenol formaldehyde based bindercompositions (requiring either prolonged cure times or increased curetemperatures).

Carbohydrate-based binder compositions are made of relativelyinexpensive precursors and are derived mainly from renewable resources.However, these binders may also require reaction conditions for curingthat are substantially different from those conditions under which thetraditional phenol formaldehyde binder system is cured.

Specifically, a versatile alternative to the above-mentioned phenolformaldehyde binders is the use of carbohydrate polyamine binders whichare polymeric binders obtained by reaction of carbohydrates withpolyamines having at least one primary amine group. These carbohydratepolyamine binders are effective substitutes for phenol formaldehydebinders, since they possess similar or superior binding characteristicsand are highly compatible to the established processes.

Typically, the carbohydrate polyamine binders are prepared as asolution, such as an aqueous solution, and are subsequently applied ontothe loosely assembled matter to be bound. The such wetted looselyassembled matter is then, for example, heat treated to cure thecarbohydrate polyamine binder.

Nonetheless, the currently available binder compositions are sometimeslinked with drawbacks such as potentially low reaction/curing rates anddissatisfactory internal bond strength and/or shelf life of the productsobtained by using the above binder compositions, and thus there is stillplenty of room for improvements to said binder compositions.

Accordingly, the technical problem underlying the present invention isto provide binder compositions which exhibit improved properties such asexcellent curing rates, longer shelf life, and improved internal bondstrength of the products obtained by using the binder compositions.

SUMMARY

In order to solve the above technical problem, as a first aspect, thepresent invention provides a binder composition comprising a polymericproduct of at least one carbohydrate component and at least one aminecomponent, wherein the at least one amine component comprises apolyethyleneimine.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows: Cure rates of binders comprising DMH andpolyethyleneimine.

FIG. 2 shows: Dynamical mechanical analysis of polyethyleneiminebinders.

FIG. 3 shows: Bond strength of polyethyleneimine binders.

FIG. 4 shows: Gel time of binder compositions comprising Lupasol

FIG. 5 shows: Gel time of binder compositions comprising Lupasol P andHMDA.

FIG. 6 shows: An interval plot of force @ peak vs. Composition Nos. 1, 5and 6.

DETAILED DESCRIPTION

According to the present invention, the term “binder composition” is notparticularly restricted and generally includes any polymeric product ofa carbohydrate component and a specific amine component of the presentinvention, which may be used as a binder, e.g. for binding looselyassembled matter, either as such or upon further modification.

According to the present invention, the at least one amine componentcomprises a polyethyleneimine. The polyethyleneimine may be a linearpolyethyleneimine, i.e. a polyethyleneimine having only two primaryamino groups at the ends of the polymer chain while having justsecondary amino groups within the chain, or a branched polyethyleneiminewhich has a mixture of primary, secondary and tertiary amino groups.According to a preferred embodiment, the polyethyleneimine is a branchedpolyethyleneimine. One advantage of branched polyethyleneimines is thatthey are generally soluble in water.

The average molecular weight of the polyethyleneimine of the presentinvention is not particularly limited. However, the average molecularweight is preferably in the range of 500 to 1,000,000 g/mol, morepreferably in the range of 5,000 to 900,000 g/mol, and most preferablyin the range of 25,000 to 800,000 g/mol. If the average molecular weightof the polyethyeleneimine is too high, problems with respect to theviscosity of the solution may arise. The average molecular weight may bedetermined by a GPC method known to those skilled in the art.

According to a preferred embodiment of the present invention, thepolyethyleneimine has a ratio of primary amino groups tosecondary+tertiary amino groups in the range of 1:2 to 1:1, morepreferably in the range of 1:1.9 to 1:1.2, and most preferably in therange of 1:1.8 to 1:1.4. In this context, the expression“secondary+tertiary amino groups” refers to the total amount ofsecondary and tertiary amino groups. If the ratio of primary aminogroups to secondary+tertiary amino groups is in the above ranges, highcuring/reaction rates can be achieved. The above ratio may be determinedby a ¹³NMR method known to those skilled in the art.

Preferably, the polyethyleneimine has a ratio of primary amino groups tosecondary amino groups to tertiary amino groups in the range of1:1.1:0.7 to 1:0.9:0.5, since high curing/reaction rates can be achievedif the above ratio is in this range. The above ratio may be determinedby a ¹³NMR method known to those skilled in the art.

According to a preferred embodiment, the polyethyleneimine has aviscosity in water at a concentration of 50 wt.-% at 25° C. of 100 to50.000 mPa·s, more preferably 1000 to 40.000 mPa·s, still morepreferably 5.000 to 30.000 mPa·s, and most preferably 11.000 to 25.000mPa·s. If the viscosity of the polyethyleneimine is below or above thesevalues, problems with respect to handling and/or reaction speed of thebinder composition may arise. The viscosity in the present invention isdetermined in accordance with ISO 2555.

According to the present invention, the term “carbohydrate component” isnot specifically restricted and generally includes any carbohydratecompound which is capable of reacting with an amine component.

The amount of the carbohydrate component used in the binder compositionof the present invention is not specifically limited and includes rangesof (based on the total amount of the binder composition) from 1 to 99wt.-%, 1 to 90 wt.-%, 1 to 80 wt.-%, 1 to 70 wt.-%, 1 to 60 wt.-%, 1 to50 wt.-%, 1 to 40 wt.-%, 1 to 30 wt.-%, 1 to 20 wt.-% and 1 to 10 wt.-%.Other specific ranges include from 20 to 95 wt.-%, 30 to 95 wt.-%, 35 to95 wt.-%, 40 to 95 wt.-%, 45 to 95 wt.-%, 50 to 95 wt.-%, and 60 to 95wt.-%.

According to one embodiment of the above-defined binder composition, theat least one carbohydrate component is selected from the groupconsisting of monosaccharides, disaccharides, polysaccharides or areaction product thereof.

For example, the carbohydrate component may be a reducing sugar. As usedherein, the term “reducing sugar” indicates one or more sugars thatcontain aldehyde groups, or that can isomerize, i.e., tautomerize, tocontain aldehyde groups, which groups may be oxidized with, for example,Cu-ions to afford carboxylic acids. According to the present invention,any such carbohydrate component may be optionally substituted, such aswith hydroxy, halo, alkyl, alkoxy, and the like. In any suchcarbohydrate component, one or more chiral centers may be present, andboth possible optical isomers at each chiral center are included in theinvention described herein. Further, it is also to be understood thatvarious mixtures, including racemic mixtures, or other diastereomericmixtures of the various optical isomers of any such carbohydratecomponent, as well as various geometric isomers thereof, may be used inone or more embodiments described herein.

Moreover, while non-reducing sugars, for instance sucrose, may not bepreferable, they may nonetheless be useful within the scope of thepresent invention by in-situ conversion to a reducing sugar. Further, itis also understood that a monosaccharide, a disaccharide, or apolysaccharide may be partially reacted with a precursor to form acarbohydrate reaction product. To the extent that the carbohydratereaction product is derived from a monosaccharide, a disaccharide, or apolysaccharide, and maintains similar reactivity with the aminecomponent to form reaction products similar to those of amonosaccharide, a disaccharide, or a polysaccharide with an aminecomponent, the carbohydrate reaction product is within the scope of termcarbohydrate component.

Preferably, any carbohydrate component should be sufficientlynonvolatile to maximize its ability to remain available for reactionwith the amine component. The carbohydrate component may be amonosaccharide in its aldose or ketose form, including a triose, atetrose, a pentose, a hexose, or a heptose; or a polysaccharide; orcombinations thereof. For example, when a triose serves as thecarbohydrate component, or is used in combination with other reducingsugars and/or a polysaccharide, an aldotriose sugar or a ketotriosesugar may be utilized, such as glyceraldehyde and dihydroxyacetone,respectively. When a tetrose serves as the carbohydrate component, or isused in combination with other reducing sugars and/or a polysaccharide,aldotetrose sugars, such as erythrose and threose; and ketotetrosesugars, such as erythrulose, may be utilized. When a pentose serves asthe carbohydrate component, or is used in combination with otherreducing sugars and/or a polysaccharide, aldopentose sugars, such asribose, arabinose, xylose, and lyxose; and ketopentose sugars, such asribulose, arabulose, xylulose, and lyxulose, may be utilized. When ahexose serves as the carbohydrate component, or is used in combinationwith other reducing sugars and/or a polysaccharide, aldohexose sugars,such as glucose (i.e., dextrose), mannose, galactose, allose, altrose,talose, gulose, and idose; and ketohexose sugars, such as fructose,psicose, sorbose and tagatose, may be utilized. When a heptose serves asthe carbohydrate component, or is used in combination with otherreducing sugars and/or a polysaccharide, a ketoheptose sugar such assedoheptulose may be utilized. Other stereoisomers of such carbohydratecomponents not known to occur naturally are also contemplated to beuseful in preparing the binder compositions as described herein. In oneembodiment, the carbohydrate component is high fructose corn syrup(HFCS).

As mentioned above, the carbohydrate component may be polysaccharide.For example, the carbohydrate component may be polysaccharide with a lowdegree of polymerization and includes e.g. molasses, starch, cellulosehydrolysates, or mixtures thereof. According to a specific example, thecarbohydrate component is a starch hydrolysate, a maltodextrin, or amixture thereof. While carbohydrates of higher degrees of polymerizationmay not be preferable, they may nonetheless be useful within the scopeof the present invention by in-situ depolymerization.

Furthermore, according to the present invention, the carbohydratecomponent may be used in combination with a non-carbohydrate polyhydroxyreactant. Examples of non-carbohydrate polyhydroxy reactants which canbe used in combination with the carbohydrate component include, but arenot limited to, trimethylolpropane, glycerol, pentaerythritol, polyvinylalcohol, partially hydrolyzed polyvinyl acetate, fully hydrolyzedpolyvinyl acetate, and mixtures thereof. For example, thenon-carbohydrate polyhydroxy reactant is sufficiently nonvolatile tomaximize its ability to remain available for reaction with a monomericor polymeric polyamine. Moreover, according to the present invention,the hydrophobicity of the non-carbohydrate polyhydroxy reactant may be afactor in determining the physical properties of a binder prepared asdescribed herein.

In a preferred embodiment of the above-defined pre-reacted bindercomposition, the at least one carbohydrate component is selected fromthe group consisting of ribose, arabinose, xylose, lyxose, glucose(dextrose), mannose, galactose, allose, altrose, talose, gulose, idose,fructose, psicose, sorbose, dihydroxyacetone, sucrose and tagatose, aswell as mixtures thereof.

According to a preferred embodiment of the present invention, the weightratio between the at least one carbohydrate component and thepolyethyleneimine is from 95:5 to 70:30.

According to one embodiment of the present invention, in the bindercomposition, the polymeric product is a product of the at least onecarbohydrate component, the at least one amine component, and at leastone additional crosslinker which is different from the amine component.The additional crosslinker is not specifically limited and includes anycrosslinking agent known to those skilled in the art. Specific examplesof the additional crosslinker include nitrogen-containing compounds suchas amines, amino acids, inorganic ammonium salts, etc. Further examplesinclude silicon-containing compounds such as silylethers, alkylsilylethers, silanes, etc. According to a preferred embodiment, theadditional crosslinker is hexamethylenediamine (NMDA).

The amount of said additional crosslinker used in the binder compositionof the present invention is not specifically limited and includes rangesof (based on the total amount of the binder composition) from 1 to 50wt.-%, 1 to 45 wt.-%, 1 to 40 wt.-%, 1 to 35 wt.-%, 1 to 30 wt.-%, 1 to25 wt.-%, 1 to 20 wt.-%, 1 to 15 wt.-%, 1 to 10 wt.-% and 1 to 5 wt.-%.Other specific ranges include from 5 to 50 wt.-%, 10 to 50 wt.-%, 15 to50 wt.-%, 20 to 50 wt.-%, 25 to 50 wt.-%, 30 to 50 wt.-%, 35 to 50wt.-%, 40 to 50 wt.-% and 45 to 50 wt.-%. According to a specificembodiment, the amount of the additional crosslinker used in the bindercomposition of the present invention is larger than the amount of the atleast one amine component.

The amount of the amine component used in the binder composition of thepresent invention is not specifically limited and includes ranges of(based on the total amount of the binder composition) from 1 to 50wt.-%, 1 to 45 wt.-%, 1 to 40 wt.-%, 1 to 35 wt.-%, 1 to 30 wt.-%, 1 to25 wt.-%, 1 to 20 wt.-%, 1 to 15 wt.-%, 1 to 10 wt.-% and 1 to 5 wt.-%.Other specific ranges include from 5 to 50 wt.-%, 10 to 50 wt.-%, 15 to50 wt.-%, 20 to 50 wt.-%, 25 to 50 wt.-%, 30 to 50 wt.-%, 35 to 50wt.-%, 40 to 50 wt.-% and 45 to 50 wt.-%.

According to a preferred embodiment of the present invention, theadditional crosslinker is hexamethylenediamine (HMDA). When the bindercomposition additionally comprises HMDA, a ratiocarbohydrate:polyethyleneimine:HMDA in the range of 78:2:20 to 74:7:19is particularly preferable. In this case, the curing/reaction rate ofthe binder composition as well as the bond strength e.g. of resultingfiber products is advantageously improved.

In a further aspect, the present invention provides a binder compositioncomprising a water-soluble pre-reacted binder and a second aminecomponent, wherein the water-soluble pre-reacted binder comprises thereaction product(s) of at least one carbohydrate component and at leastone first amine component, wherein the ratio of the reactivenitrogen-containing groups of the at least one first amine component tothe carbonyl groups of the at least one carbohydrate component issubstoichiometric such that there is no full conversion of the at leastone carbohydrate component, and wherein the second amine componentcomprises a polyethyleneimine.

Herein, the term “reactive nitrogen-containing group” is notparticularly restricted and includes any nitrogen-containing groups inthe first amine component which are capable of reacting with thecarbohydrate component. Specifically, examples of such reactivenitrogen-containing groups include primary, secondary, tertiary andquaternary amino groups.

As used herein, the expression “that there is no full conversion of theat least one carbohydrate component” means that some of the initialcarbonyl groups of the carbohydrate component have not reacted with thefirst amine component and are still present, since the carbonyl groupsof the carbohydrate component are in excess with respect to the reactivenitrogen-containing groups of the first amine component. According to apreferred embodiment, the pre-reacted binder as defined above comprisesat least 10% of the initial carbonyl groups provided by the carbohydratecomponent. Further examples of the number of unreacted carbonyl groupsin the pre-reacted binder include at least 15%, at least 20%, at least25%, at least 30%, at least 35%, at least 40%, at least 50%, at least60% or at least 75% of the carbonyl groups present in the carbohydratecomponent before reaction with the first amine component.

According to the present invention, the term “pre-reacted binder” is notparticularly restricted and generally includes any chemical compositionobtained by reacting a carbohydrate component and an amine component,which may be used as a binder, e.g. for binding loosely assembledmatter, either as such or upon further modification. The “at least onecarbohydrate component” and “the (second) amine component comprising apolyethyeneimine” are the same as described above.

Further, herein the “first amine component” is not particularly limitedand includes any chemical compound, or mixture of compounds, whichcontains at least one amino group and which is capable of reacting withthe at least one carbohydrate component to form a pre-reacted binder.According to one embodiment, in the pre-reacted binder, the at least onefirst amine component is NH₃, an inorganic amine or an organic aminecomprising at least one primary amino group, as well as salts thereof.For example, as the first amine component NH₃ may be used as such (e.g.in form of an aqueous solution), as well as any type of inorganic andorganic ammonium salts, as long as these salts are capable of reactingwith the carbohydrate component defined above. Specific examples ofinorganic ammonium salts include ammonium sulfate (AmSO₄), ammoniumchloride, and ammonium nitrate.

According to the present invention, the first amine component may be apolyamine. Herein, the term “polyamine” includes any organic compoundhaving two or more amino groups, which may independently be substitutedor unsubstituted.

For example, the polyamine may be a primary polyamine. As used herein, a“primary polyamine” is an organic compound having two or more primaryamino groups (—NH₂). Herein, the term “primary amino group” alsoincludes amino groups in their salt forms, e.g. ammonium groups. Withinthe scope of the term primary polyamine are those compounds which can bemodified in situ or isomerize to generate a compound having two or moreprimary amino groups (—NH₂).

According to one embodiment of the present invention, the primarypolyamine may be a molecule having the formula H₂N-Q-NH₂, wherein Q isan alkyl, cycloalkyl, heteroalkyl, or cycloheteroalkyl, each of whichmay be optionally substituted. For example, Q may be an alkyl groupselected from a group consisting of C₂-C₂₄, an alkyl selected from agroup consisting of C₂-C₉, an alkyl selected from a group consisting ofC₃-C₇. According to a preferred embodiment, Q is a C₆ alkyl. Accordingto another embodiment, Q may be a cyclohexyl, cyclopentyl or cyclobutyl,or a benzyl group.

As used herein, the term “alkyl” includes a chain of carbon atoms, whichmay optionally be branched. As used herein, the terms “alkenyl” and“alkynyl” independently include a chain of carbon atoms, which mayoptionally be branched, and include at least one double bond or triplebond, respectively. It is to be understood that alkynyl may also includeone or more double bonds. It is to be further understood that alkyl isadvantageously of limited length, including C₁-C₂₄, C₁-C₁₂, C₁-C₈,C₁-C₆, and C₁-C₄. It is to be further understood that alkenyl and/oralkynyl may each be advantageously of limited length, including C₂-C₂₄,C₂-C₁₂, C₂-C₈, C₂-C₆, and C₂-C₄. In particular, shorter alkyl, alkenyl,and/or alkynyl groups may add less lipophilicity to the compound andaccordingly will have different reactivity towards the carbohydratecomponent and solubility in a binder solution.

As used herein, the term “cycloalkyl” includes a chain of carbon atoms,which may optionally be branched, where at least a portion of the chainis cyclic. Moreover, according to the present invention it is to benoted that “cycloalkylalkyl” is regarded as a subset of cycloalkyl, andthat the term “cycloalkyl” also includes polycyclic structures. Forexample, such cycloalkyls include, but are not limited to, cyclopropyl,cyclopentyl, cyclohexyl, 2-methylcyclopropyl, cyclopentyleth-2-yl,adamantyl, and the like. As used herein, the term “cycloalkenyl”includes a chain of carbon atoms, which may optionally be branched, andincludes at least one double bond, where at least a portion of the chainis cyclic. According to the present invention, said at least one doublebond may be in the cyclic portion of cycloalkenyl and/or the non-cyclicportion of cycloalkenyl. Moreover, it is to be understood thatcycloalkenylalkyl and cycloalkylalkenyl are each regarded as subsets ofcycloalkenyl. Moreover, according to the present invention “cycloalkyl”may be polycyclic. Examples of such cycloalkenyls include, but are notlimited to, cyclopentenyl, cyclohexylethen-2-yl, cycloheptenylpropenyl,and the like. Furthermore, the chain forming cycloalkyl and/orcycloalkenyl is advantageously of limited length, including C₃-C₂₄,C₃-C₁₂, C₃-C₈, C₃-C₆, and C₅-C₆. According to the present invention,shorter alkyl and/or alkenyl chains forming cycloalkyl and/orcycloalkenyl, respectively, may add less lipophilicity to the compoundand accordingly will have different behavior.

As used herein, the term “heteroalkyl” includes a chain of atoms thatincludes both carbon and at least one heteroatom, and is optionallybranched. Examples of such heteroatoms include nitrogen, oxygen, andsulfur. In certain variations, said hetero-atoms also includephosphorus, and selenium. In one embodiment, a heteroalkyl is apolyether. As used herein, the term “cycloheteroalkyl” includingheterocyclyl and heterocycle, includes a chain of atoms that includesboth carbon and at least one heteroatom, such as heteroalkyl, and mayoptionally be branched, where at least a portion of the chain is cyclic.Similarly, examples of cycloheteroalkyl include, but are not limited to,tetrahydrofuryl, pyrrolidinyl, tetrahydropyranyl, piperidinyl,morpholinyl, piperazinyl, homopiperazinyl, quinuclidinyl, and the like.

Herein, the term “optionally substituted” includes the replacement ofhydrogen atoms with other functional groups on the radical that isoptionally substituted. Such other functional groups illustrativelyinclude, but are not limited to, amino, hydroxyl, halo, thiol, alkyl,haloalkyl, heteroalkyl, aryl, arylalkyl, arylheteroalkyl, nitro,sulfonic acids and derivatives thereof, carboxylic acids and derivativesthereof, and the like. Illustratively, any of amino, hydroxyl, thiol,alkyl, haloalkyl, heteroalkyl, aryl, arylalkyl, arylheteroalkyl, and/orsulfonic acid is optionally substituted.

For example, the primary polyamine may be a diamine, triamine,tetraamine, or pentamine. According to one embodiment, the polyamine isa triamine selected from a diethylenetriamine, 1-piperazineethaneamine,or bis(hexamethylene)triamine. In another embodiment, the polyamine is atetramine, for example triethylenetetramine. In another embodiment, thepolyamine is a pentamine, for example tetraethylenepentamine.

One aspect of the primary polyamine is that it may possess low sterichindrance. For example, 1,2-diaminoethane, 1,4-diaminobutane,1,5-diaminopentane, 1,6-diaminohexane, 1,12-diaminododecane,1,4-diaminocyclohexane, 1,4-diaminobenzene, diethylenetriamine,triethylenetetramine, tetraethylenepentamine, 1-piperazine-ethaneamine,2-methyl-pentamethylenediamine, 1,3-pentanediamine, andbis(hexamethylene)triamine, as well as 1,8-diaminooctane have low sterichindrance within the scope of the present invention. According to apreferred embodiment of the pre-reacted binder as defined above, thefirst amine component is the primary polyamine 1,6-diaminohexane(hexamethylenediamine, HMDA). In a further embodiment, the first aminecomponent is 1,5-diamino-2-methylpentane(2-methyl-pentamethylenediamine).

In another embodiment, the first amine component is the primarypolyamine polyether-polyamine. For example, according to the presentinvention, said polyether-polyamine is a diamine or a triamine. In oneembodiment, the polyether-polyamine is a trifunctional primary aminehaving an average molecular weight of 440 known as Jeffamine T-403Polyetheramine (Huntsman Corporation).

In a further embodiment, the first amine component may include apolymeric polyamine. For example, polymeric polyamines within the scopeof the present invention include chitosan, polylysine, polyethylenimine,poly(N-vinyl-N-methyl amine), polyaminostyrene and polyvinylamines. In aspecific example, the first amine component comprises a polyvinyl amine.As used herein, the polyvinyl amine can be a homopolymer or a copolymer.

In a specific embodiment, the first and second amine components may bethe same.

Herein, the term “water-soluble” is not specifically restricted andincludes all grades of water-solubility of the pre-reacted binder asdefined above. In particular, the term “water-soluble” includeswater-solubility at 20° C. of 100 g/l or more, 150 g/l or more, 200 g/lor more, or 250 g/l or more. For example, the term “water-soluble” mayinclude a water-solubility of the pre-reacted binder as defined above of300 g/l or more, 400 g/l or more, 500 g/l or more or 600 g/l or more (at20° C.). Also virtual infinitive water-solubility may be regarded to bewithin the scope of the present invention.

In this context, the expression “water-insoluble” according to thepresent invention relates to cases where the pre-reacted binder asdefined above is essentially not soluble in water at 20° C. For example,the term insoluble includes a water-solubility at 20° C. of 50 g/l orless, 40 g/l or less, 30 g/l or less, or 20 g/l or less. Preferably, theterm water-insoluble includes cases of water-solubility of 10 g/l orless, 5 g/l or less, 1 g/l or less or 0.1 g/l or less.

According to the present invention, an aqueous solution containing 70wt.-% of the above-defined pre-reacted binder preferably has a viscosityat 20° C. of at most 2000 mPa·s, wherein the viscosity of said aqueoussolution does not increase by more than 500 mPa·s when left to stand at20° C. for 12 hours.

For example, an aqueous solution containing 70 wt.-% of theabove-defined pre-reacted binder (i.e. an aqueous solution containing70% wt.-% of solids) may have an initial viscosity after its preparationof 100 to 1500 mPa·s, of 150 to 1200 mPa·s, of 200 to 800 mPa·s, of 220to 600 mPa·s, or of 250 to 400 mPa·s. From the viewpoint of handling, apreferred viscosity is in the range of 280 to 350 mPa·s. Viscosity maybe measured using a LV-Torque Brookfield Viscometer, spindle LV-63 at 60rpm.

Moreover, the viscosity of said aqueous solution should preferably notincrease by more than 500 mPa·s when left to stand at 20° C. for 24hours, 48 hours, 72 hours or 96 hours. According to a further preferredembodiment, the viscosity of said aqueous solution should not increaseby more than 500 mPa·s within a week, 10 days, 12 days or two weeks.Longer periods, such as three or four weeks, or even two, three or moremonths, where the viscosity will not increase by more than 500 mPa·s areeven more preferable.

According to a further embodiment, the amount by which the viscosityincreases within the first 12 hours when leaving an 70 wt.-% aqueoussolution of the pre-reacted binder to stand at 20° C. should preferablynot exceed 450 mPa·s, or 400 mPa·s or even 350 mPa·s. Preferredincreases in viscosity include increases of 300 mPa·s or less, 280 mPa·sor less, 250 c mPa·s or less and 200 mPa·s or less.

According to the present invention, the above-defined time periods andincreases in viscosity are not limited to the examples mentioned aboveand may be freely combined. For example, preferably, the above-mentioned70 wt.-% aqueous solution of the pre-reacted binder does not increase inviscosity by more than 300 mPa·s within the first 48 hours after itspreparation, or more than 400 mPa·s within two weeks after itspreparation. Generally, if the viscosity of a respective aqueoussolution becomes too high, e.g. caused by gelling, the pre-reactedbinder may become unusable.

In one embodiment, the preparation of the pre-reacted binder is carriedout in a solvent, such as water, to directly yield a binder solutionusable for storage, shipping and then as a basis for preparing the finalbinder composition by addition of the second amine component. Forexample, the pre-reacted binder may be prepared in a concentratedaqueous solution of the carbohydrate component and the first aminecomponent. The thus obtained concentrated pre-reacted binder solutionmay then be used, for example, at a later time and/or a different place,e.g. by dilution and addition of the second amine component, as aneffective binder for consolidating loosely assembled matter.

The term “solvent” used herein is not particularly restricted andincludes any solvent which may be used to carry out a reaction betweenthe carbohydrate component and the amine component. For example, thesolvent may be water, an organic solvent or mixtures thereof. Examplesof organic solvents include alcohols, ethers, esters, ketones,aldehydes, alkanes and cycloalkanes.

According to one embodiment of the above-defined pre-reacted binder, theratio of carbonyl groups in the carbohydrate component to reactivenitrogen-containing groups in the first amine component is 5:1 to 1:2 or5:1 to 1:1. For example, the ratio of carbonyl groups to reactivenitrogen-containing groups may be 5:1 to 1:1.8, 5:1 to 1:1.5, 5:1 to1:1.2, 5:1 to 1:1, 5:1 to 1:0.8 and 5:1 to 1:0.5. Further examplesinclude ratios such as 4:1 to 1:2, 3.5:1 to 1:2, 3:1 to 1:2, 2.5:1 to1:2, 2:1 to 1:2 and 1.5:1 to 1:2. According to the present invention,the upper and lower borders of the above-mentioned ratios may be freelycombined.

The pre-reacted binder as defined above may be obtained by reacting in asolvent the at least one carbohydrate component with the at least onefirst amine component at a temperature of at least 10° C. for a periodof at least 5 minutes.

The temperature at which the pre-reacted binder is prepared is, however,not specifically restricted and includes temperatures in the range of 10to 200° C., 15 to 180° C., 20 to 150° C. or 25 to 130° C. For example,the reaction temperature may range from 20 to 120° C., 25 to 110° C., 30to 100° C. or 35 to 90° C. Specific examples of the temperature rangeinclude 40 to 90° C., 45 to 85° C. and 50 to 75° C. According to thepresent invention, the temperature at which the pre-reacted bindercomposition is prepared is not limited to the above ranges, and theupper and lower values of said ranges may be freely combined.

Similarly, the duration of the reaction to obtain the pre-reacted binderis not specifically restricted and includes durations of 5 to 240minutes, 5 to 210 minutes, 5 to 180 minutes, 5 to 120 minutes, 5 to 90minutes, 5 to 75 minutes 5 to 60 minutes, 5 to 40 minutes, 5 to 30minutes and 5 to 25 minutes. Further examples include durations of 5 to240 minutes, 10 to 240 minutes, 15 to 240 minutes, 20 to 240 minutes, 25to 240 minutes, 30 to 240 minutes, 40 to 240 minutes, 45 to 240 minutes,60 to 240 minutes, 120 to 240 minutes and 180 to 240 minutes. However,durations of up to one, two, three, four, five and six days, as well asdurations of one, two or three weeks may also be reasonable within thescope of the present invention. According to the present invention, theduration for preparing the pre-reacted binder as defined above is notlimited to the above examples and the upper and lower values of saidranges may be freely combined herein.

According to one embodiment, the above-defined pre-reacted binderfurther reacts with the second amine component to yield one or moremelanoidins as a water-insoluble composition. In the present invention,the pre-reacted binder may function as a precursor or intermediate whichmay be further reacted with the second amine component to obtain apolymeric binder. For example, this polymeric binder contains highmolecular weight melanoidins as Maillard reaction products which areessentially water-insoluble.

According to a further embodiment, the molar ratio between thecarbohydrate component and the first amine component in the pre-reactedbinder is 0.5:1 to 30:1. Examples of further molar ratios include ratiosof 0.7:1 to 25:1, 1:1 to 22:1, 1.5:1 to 20:1, 2:1 to 15:1, 2.5:1 to 10:1or 3:1 to 8:1. However, according to the present invention, the molarratio of carbohydrate component to first amine component is not limitedto said ranges and the above upper and lower borders may be freelycombined.

Further, the pre-reacted binder may comprise one or more of aglycolaldehyde, glyceraldehyde, 2-oxopropanal, acetol, dihydroxyacetone,acetoin, butanedione, ethanal, glucosone, 1-desoxyhexosulose,3-desoxyhexosulose, 3-desoxypentosulose, 1,3-didesoxyhexosulose,glyoxal, methylglyoxal and diacetyl, wherein an aqueous solutioncontaining 70 wt.-% of said pre-reacted binder has a viscosity at 20° C.of at most 2000 mPa·s, and the viscosity of said aqueous solution doesnot increase by more than 500 mPa·s when left to stand at 20° C. for 12hours.

According to the present invention, the total content of said one ormore above-mentioned compounds may be at least 10 wt.-%, at least 20wt.-%, at least 30 wt.-%, at least 40 wt.-%, at least 50 wt.-%, at least60 wt.-%, or at least 75 wt.-% of the pre-reacted binder.

According to a preferred embodiment, the above-defined pre-reactedbinder has an average molecular weight in the range of 200 to 5000g/mol. According to the present invention, the average molecular weightof the pre-reacted binder composition may range from 300 to 4500 g/mol,from 400 to 4000 g/mol, from 450 to 3500 g/mol, from 500 to 300 g/mol orfrom 600 to 1500 g/mol. However, the average molecular weight of thepre-reacted binder is not limited to said ranges and the upper and lowervalues thereof may be freely combined.

According to the present invention, the pre-reacted binder may changeover time in its chemical composition by continuing the reaction betweenthe carbohydrate component and the first amine component. For example,even at relatively low temperatures, such as room temperature (20° C.)or below, the Maillard-type reactions may continue between thecarbohydrate component and the first amine component towards theformation of melanoidins. As a consequence, ageing of the pre-reactedbinder may lead to an accelerated final curing process of the binderand/or to an improved bond strength.

According to a preferred embodiment of the binder composition comprisinga water-soluble pre-reacted binder and a second amine component, thesecond amine component additionally comprises hexamethylenediamine(HMDA). When the second amine component additionally compriseshexamethylenediamine, a ratio pre-react:polyethyleneimine:HMDA in therange of 84:7:9 to 88:3:9 is particularly preferable. In this case, thecuring/reaction rate of the binder composition as well as the bondstrength e.g. of resulting fiber products is advantageously improved.

Various additives can be incorporated into the binder compositions ofthe present invention. These additives give the binders of the presentinvention additional desirable characteristics. For example, the bindermay include a silicon-containing coupling agent. Many silicon-containingcoupling agents are commercially available from the Dow-CorningCorporation, Evonik Industries, and Momentive Performance Materials.Illustratively, the silicon-containing coupling agent includes compoundssuch as silylethers and alkylsilyl ethers, each of which may beoptionally substituted, such as with halogen, alkoxy, amino, and thelike. In one variation, the silicon-containing compound is anamino-substituted silane, such as, gamma-aminopropyltriethoxy silane(SILQUEST A-1101; Momentive Performance Materials, CorporateHeadquarters: 22 Corporate Woods Boulevard, Albany, N.Y. 12211 USA). Inanother variation, the silicon-containing compound is anamino-substituted silane, for example, aminoethylaminopropyltrimethoxysilane (Dow Z-6020; Dow Chemical, Midland, Mich.; USA). In anothervariation, the silicon-containing compound isgamma-glycidoxypropyltrimethoxysilane (SILQUEST A-187; Momentive). Inyet another variation, the silicon-containing compound is anaminofunctional oligomeric siloxane (HYDROSIL 2627, Evonik Industries,379 Interpace Pkwy, Parsippany, N.J. 07054).

The silicon-containing coupling agents are typically present in thebinder in the range from about 0.1 percent to about 1 percent by weightbased upon the dissolved binder solids (i.e., about 0.05% to about 3%based upon the weight of the solids added to the aqueous solution).These silicone containing compounds enhance the ability of the binder toadhere to the matter the binder is disposed on, such as glass fibers.Enhancing the binder's ability to adhere to the matter improves, forexample, its ability to produce or promote cohesion in non- orloosely-assembled substance(s).

In another illustrative embodiment, a binder of the present inventionmay include one or more corrosion inhibitors. These corrosion inhibitorsprevent or inhibit the eating or wearing away of a substance, such as,metal caused by chemical decomposition brought about by an acid. When acorrosion inhibitor is included in a binder of the present invention,the binder's corrosivity is decreased as compared to the corrosivity ofthe binder without the inhibitor present. In one embodiment, thesecorrosion inhibitors can be utilized to decrease the corrosivity of themineral fiber-containing compositions described herein. Illustratively,corrosion inhibitors include one or more of the following, a dedustingoil, or a monoammonium phosphate, sodium metasilicate pentahydrate,melamine, tin(II) oxalate, and/or methylhydrogen silicone fluidemulsion. When included in a binder of the present invention, corrosioninhibitors are typically present in the binder in the range from about0.5 percent to about 2 percent by weight based upon the dissolved bindersolids.

A further aspect of the present invention relates to a method ofmanufacturing a collection of matter bound by a polymeric bindercomprising the steps: (i) providing a collection of matter, (ii)providing the above-defined binder composition as a solution ordispersion, (iii) applying the solution or dispersion of step (ii) tothe collection of matter, and (iv) applying heat to the collection ofmatter containing said solution or dispersion to cure the bindercomposition.

Herein, the term “collection of matter” is not particularly restrictedand includes any collection of matter which comprises fibers selectedfrom the group consisting of mineral fibers (slag wool fibers, rock woolfibers, or glass fibers), aramid fibers, ceramic fibers, metal fibers,carbon fibers, polyimide fibers, polyester fibers, rayon fibers, andcellulosic fibers. Further examples of a collection of matter includeparticulates such as coal, sand or glass fibers, cellulosic fibers, suchas wood shavings, sawdust, wood pulp, or ground wood, as well as othernatural fibers such as jute, flax, hemp, and straw; wood veneers;facings, wood facings, particles, woven or non-woven materials (e.g.comprising fibers, notably of the type(s) referred to above).

According to the present invention, step (iv) of applying heat to thecollection of matter as defined in the above method is not particularlyrestricted and includes, for example, heating in an oven at atemperature of 100° C. to 350° C., depending on the type of matter, theamount of binder and other conditions.

Binders in accordance with the present invention may be used as bindersin articles selected from the group consisting of: thermal insulationmaterials; mineral wool insulation (including glass wool insulation andstone wool insulation); wood boards; fiberboards; wood particle boards;chip boards; orientated strand board; medium density fiberboards; highpressure laminates.

The binder compositions of the present invention advantageously overcomea variety of drawbacks known from common carbohydrate-based binders.Particularly, binder compositions of the present invention result inaccelerated cure times, prolonged shelf life, and superior bond strengthof resulting products. Moreover, the binder compositions of the presentinvention require a surprisingly low addition percentage and anadvantageously low activation temperature for the curing process.

The present invention will be further illustrated in the followingexamples, without limitation thereto.

Example 1: Cure Rates of Polyethyleneimine with DMH

Various binders comprising polyethyleneimine and dextrose monohydrate(DMH) were prepared in water (total solids made: 22.5%) at roomtemperature according to the compositions given in FIG. 1.

Subsequently, the resulting binder compositions were compared to binderscomprising hexamethylendiamine (HMDA) and DMH. At 105° C., it wasobserved that binders comprising more than 10 wt.-% of polyethyleneiminehave higher cure rates than binders comprising HMDA (cf. FIG. 1).

Moreover, a dynamical mechanical analysis (DMA) was performed on bindercompositions to test the stiffness of the binder over a range oftemperature. The DMA is carried out by soaking a filter paper in therespective binder composition, cutting a piece of the filter soaked inthe binder, and then carefully attaching said filter in the DMA testingapparatus. Then, over a range of temperature, the DMA testing apparatusvibrates the piece of filter and measures and records the force requiredto do so. The respective graph (cf. FIG. 2) then shows the temperatureat which a binder is cured, since at this temperature the binder/soakedfilter gets stiffer. FIG. 2 clearly shows that the activationtemperature of binders comprising polyethyleneimine is lower than thatof binders comprising HMDA (cf. FIG. 2, in which: “FRU” means fructose;“PR 20 min 60C” means pre-reacted for 20 min at 60° C.; “Ecose C Std” is“40% DMH+40% fructose+10% HMDA, pre-reacted for 30 min at 60° C.”).

Example 2: Bond Strength Test

Various binders were tested for their bond strength using a veil test,which shows the strength of a binder. In the veil test, a respectivebinder composition is prepared (about 4% total solids made), a binderfree veil is soaked in the respective binder composition, afterwardscured at 200° C., optionally weathered in an autoclave, and then testedwith a tensiometer. The resulting values (N/mm²) indicate the bondstrength of the respective cured binder composition.

As can be taken from the results shown in FIG. 3, those binderscomprising 10%, 20% or 30% of polyethyleneimine resulted in a higherbond strength when compared to a standard binder comprising 30% of HMDA.

Example 3: Solids Made Vs. Solids Baked Out

Two different binder compositions (all amounts given in wt.-%)comprising polyethyleneimine were cured at 140° C. for 2 hours, and thefactor “solids made on solids baked out” was determined. In thiscontext, “solids made” relates to the amount of solids added in a binderformulation when prepared, whereas “solids baked out” relates to theremaining solids after the binder has been cured. When the condensationreactions take place during the polymerization of a binder, solids bakedout are lower than solids made.

Binder Solids Solids composition made baked out Factor 45% DMH + 67.5%51.84% 1.3 45% fructose + 10% polyethyleneimine 40% DMH + 67.5% 51.72%1.3 40% fructose + 20% polyethyleneimine

It was observed that the binder compositions comprisingpolyethyleneimine show an advantageously low factor of 1.3, whereasconventional binder compositions comprising ammonia or HMDA show factorsof 1.5 and 1.4, respectively. Accordingly, in a binder compositioncomprising polyethyleneimine less water is lost during curing than inconventional binder compositions. Such a low Factor is advantageous e.g.in the manufacture of timber board products.

Example 4: Shelf Life

The binder compositions of Example 3 comprising polyethyleneimine show alow factor “solids made on solids baked out”. Therefore, due to thehigher resulting solids baked out, it is possible to preparecompositions having lower solids content.

Accordingly, the binder composition comprising 20 wt.-% ofpolyethyleneimine of Example 3 gelled after four days, while the bindercomposition comprising 10 wt.-% of polyethyleneimine of Example 3remains even liquid after more than four days at room temperature, whichis highly superior when compared to the shelf life of a conventionalbinder composition comprising HMDA and no pre-react, which gels straightaway due to hydrogen bonding.

Example 5: Characteristics of Binder Compositions Comprising Lupasol

In the following, binder compositions comprising variouspolyethyleneimines (PEI) sold under the brand name Lupasol by BASF weretested with respect to cure rates and bond strength.

Average Ratio primary/ Viscosity molecular secondary/ PEI (mPa · s) atweight tertiary No. Brand name concentration (g/mol) amino groups 1Lupasol P 25.000 at 750.000 1:1.07:0.77 50 wt.-% 2 Lupasol FG 5.000 at800 1:0.82:0.53 99 wt.-% 3 Lupasol PS 1.700 at 750.000 1:1.07:0.77 33wt.-% 4 Lupasol HF 11.000 at 25.000 1:1.20:0.76 56 wt.-% 5 Lupasol G1001.100 at 5.000 1:1.05:0.76 50 wt.-%

Example 5.1: Gel Time of Binder Compositions Comprising Various Kinds ofLupasol

The kinetics of various binder compositions each comprising apre-reacted binder (41.0 wt.-% DMH+41.0 wt.-% fructose+10.3 wt.-% HMDA)and 7.7 wt.-% of one of the above-defined polyethyleneimines No. 1 to 5were characterized with a gel test, using Gelnorm (cf. FIG. 4). In thiscontext, “Gelnorm” is a gel timer composed of a heating unit and atimer. The binder composition is poured into a test tube inserted in theheating unit, set at 100° C. A rod connected to the time is plunged inthe binder. During heating, the rod goes up and down in the bindersolution. When the binder gels (due to polymerization), the rod cannotmove anymore, and the timer stops to display the gel time.

As FIG. 4 clearly shows, particularly those binder compositionscomprising polyethyleneimines No. 1 and 2 show advantageously fast geltimes.

Example 5.2: Gel Time of Binder Compositions Comprising Lupasol P andHMDA

A pre-reacted binder (PR) comprising 44.44 wt.-% DMH+44.44 wt.-%fructose+11.11 wt.-% HMDA was prepared (pre-reacted for 20 min at 60°C.).

Thereafter, several binder compositions comprising the above pre-reactedbinder, Lupasol P and HMDA were characterized with the above-describedgel test. As a reference, a binder composition comprising the abovepre-reacted binder and HMDA without Lupasol P was also characterized.The tested binder compositions are listed in the following table:

Composition Components in Amount of Amount of Amount of Amount of No.wt.-% pre-react (g) HMDA (g) Lupasol P (g) water (g) 1 81.8% PR + 32.147.14 10.71 (reference) 18.2% HMDA 2 81.8% PR + 32.14 7.86 7.86 18.2%Lupasol P 3 90% PR + 35.36 5.5 9.14 10% Lupasol P 4 90% PR + 35.36 1.962.75 9.92 5% HMDA + 5% Lupasol P 5 85.7% PR + 33.66 3.74 2.62 9.97 9.5%HMDA + 4.8% Lupasol P 6 87.3% PR + 34.33 3.81 1.6 10.25 9.7% HMDA + 3%Lupasol P 7 84.1% PR + 34.33 3.67 3.6 9.39 9.3% HMDA + 6.6% Lupasol P

The results of the gel test are depicted in FIG. 5. Compositions No. 5and 7 (containing 4.8 wt.-% and 6.6 wt.-% of Lupasol P, respectively)react faster than the fastest standard binder composition (CompositionNo. 1, comprising only HMDA as amine component). Comparing CompositionsNo. 1 and No. 5, it becomes evident that replacing some of the HMDA byeven a smaller amount of Lupasol P advantageously increases the reactionrate.

When increasing the solids content, the viscosity increases as the geltime decreases. For example, composition No. 5 can be conveniently usedat up to 60% solids made. However, at 65% solids made, the viscosity ofComposition No. 5 is already high (above 500 mPa·S).

Example 5.3: Strength of a Binder Composition Comprising Lupasol P

Due to its polymeric structure, an important advantage for usingpolyethyleneimine is the increase in strength it generates. Whencomparing Compositions No. 5 and 6, i.e. compositions in which some ofthe HMDA has been replaced by Lupasol P, with Composition No. 1 (HMDA,no PEI), the addition of even small quantities of Lupasol Padvantageously increases the strength by 35% and 50%, respectively (cf.FIG. 6). In the present case, the strength measured is the “strength atpeak”, i.e. the strength required with a testometric to break the veils(cf. Example 2) made with the binder formulations described.

Coincidentally, when performing the veil test as described in Example 2with Compositions Nos. 1, 5 and 6, the veil's LOI also increases withaddition of Lupasol P. In this context, LOI is the “Loss on Ignition”,which is determined according to EN 13820:2003. Advantageously, increasein LOI generally also results in a strength improvement as well.

1.-15. (canceled)
 16. A method of manufacturing an article selected fromthe group consisting of: thermal insulation materials; mineral woolinsulation; wood boards; fiberboards; wood particle boards; chip boards;oriented strand board; medium density fiberboards; high pressurelaminates; non-woven materials comprising fibers selected from the groupconsisting of mineral fibers, slag wool fibers, rock wool fibers, glassfibers, aramid fibers, ceramic fibers, metal fibers, carbon fibers,polyimide fibers, polyester fibers and rayon fibers; the articlecomprising a collection of matter bound by a polymeric binder, themethod comprising the steps: (i) providing the collection of matter,(ii) applying a solution or dispersion of a binder composition step (ii)to the collection of matter, and (iii) applying heat to the collectionof matter containing said solution or dispersion to cure the bindercomposition to form the article, characterized in that the bindercomposition comprises a polymeric product of at least one reducing sugarand at least one amine component, wherein the at least one aminecomponent comprises a branched polyethyleneimine having an averagemolecular weight in the range of 5,000 to 900,000 g/mole.
 17. The methodof claim 16, wherein the polyethyleneimine has a ratio of primary aminogroups to the sum of secondary and tertiary amino groups in a range of1:2 to 1:1.
 18. The method of claim 16, wherein the polyethyleneiminehas a ratio of primary amino groups to secondary amino groups totertiary amino groups in a range of 1:1.1:0.7 to 1:0.9:0.5.
 19. Themethod of claim 16, wherein the polyethyleneimine has a viscosity inwater at a concentration of 50 wt.-% (25° C.) in a range of 100 to50,000 mPa·s.
 20. The method of claim 16, wherein the at least onereducing sugar is selected from the group consisting of a reducing sugarobtained by in-situ conversion of a non-reducing sugar, monosaccharides,disaccharides, polysaccharides and reaction products thereof.
 21. Themethod claim 16, wherein the branched polyethyleneimine has an averagemolecular weight in the range of 25,000 to 800,000 g/mole.
 22. Themethod of claim 20, wherein the at least one reducing sugar is selectedfrom the group consisting of ribose, arabinose, xylose, lyxose, glucose(dextrose), mannose, galactose, allose, altrose, talose, gulose, idose,fructose, psicose, sorbose, dihydroxyacetone, sucrose, tagatose andmixtures thereof.
 23. The method of claim 16, wherein the weight ratiobetween the at least one reducing sugar and the amine component is inthe range of 95:5 to 70:30.
 24. The method of claim 16, wherein thepolymeric product is a product of the at least one reducing sugar, theat least one amine component, and at least one additional crosslinkerwhich is different from the amine component.
 25. The method of claim 24,wherein the additional crosslinker is selected from the group consistingof nitrogen-containing compounds, amino acids and inorganic ammoniumsalts.
 26. The method of claim 24, wherein the additional crosslinker ishexamethylenediamine (HMDA).
 27. The method of claim 26, wherein theratio of reducing sugar:polyethyleneimine:HMDA is in a range of 78:2:20to 74:7:19.
 28. The method of claim 16, wherein the collection of matteris selected from the group consisting of mineral fibers, slag woolfibers, rock wool fibers, glass fibers, aramid fibers, ceramic fibers,metal fibers, carbon fibers, polyimide fibers, polyester fibers, rayonfibers and cellulosic fibers.
 29. The method of claim 28, wherein thecellulosic fibres comprise matter selected from the group consisting ofwood shavings, sawdust, wood pulp, ground wood, jute, flax, hemp andstraw.